WO1996031262A2 - Conversion en phase liquide d"une source de dioxyde de sulfure en acide sulfurique - Google Patents

Conversion en phase liquide d"une source de dioxyde de sulfure en acide sulfurique Download PDF

Info

Publication number
WO1996031262A2
WO1996031262A2 PCT/CA1996/000196 CA9600196W WO9631262A2 WO 1996031262 A2 WO1996031262 A2 WO 1996031262A2 CA 9600196 W CA9600196 W CA 9600196W WO 9631262 A2 WO9631262 A2 WO 9631262A2
Authority
WO
WIPO (PCT)
Prior art keywords
sulfuric acid
liquid phase
conversion
concentration
source
Prior art date
Application number
PCT/CA1996/000196
Other languages
English (en)
Other versions
WO1996031262A3 (fr
Inventor
Robert N. O'brien
Original Assignee
Catalytic Sulphur Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Catalytic Sulphur Corporation filed Critical Catalytic Sulphur Corporation
Priority to PL96322447A priority Critical patent/PL322447A1/xx
Priority to AU51406/96A priority patent/AU704392B2/en
Priority to BR9607990-8A priority patent/BR9607990A/pt
Priority to JP8529813A priority patent/JPH11503105A/ja
Priority to CA002216432A priority patent/CA2216432C/fr
Priority to EP96907976A priority patent/EP0839117A2/fr
Publication of WO1996031262A2 publication Critical patent/WO1996031262A2/fr
Publication of WO1996031262A3 publication Critical patent/WO1996031262A3/fr
Priority to NO974468A priority patent/NO974468L/no

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/69—Sulfur trioxide; Sulfuric acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D1/00—Evaporating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/507—Sulfur oxides by treating the gases with other liquids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/69—Sulfur trioxide; Sulfuric acid
    • C01B17/74—Preparation
    • C01B17/76—Preparation by contact processes
    • C01B17/775—Liquid phase contacting processes or wet catalysis processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/50—Inorganic acids
    • B01D2251/504—Nitric acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/50—Inorganic acids
    • B01D2251/506—Sulfuric acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/304—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/306—Organic sulfur compounds, e.g. mercaptans
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds

Definitions

  • This invention relates to a process for producing sulfuric acid in the liquid phase from a source of sulfur dioxide.
  • Concentrated sulfuric acid is a major chemical commodity used in a variety of industries, ranging from heavy industry through to fine chemical manufacture.
  • Sulfuric acid is primarily made by two distinct commercial processes. They are commonly referred to as the lead chamber process and the Contact Process. The more advanced of the two processes is the Contact Process.
  • the Contact Process There have been several advances in the Contact Process technology, such as described in U.S Patent 5,118,490, where a process is capable of treating wet sulfur dioxide gases which are catalytically converted to sulfur trioxide gases. In the presence of water, the generated S0 3 produces sulfuric acid.
  • One source for the wet sulfur dioxide gas is the combustion of hydrogen sulphide.
  • Hydrogen sulphide and other possibly harmful and/or valuable components can be produced by metal smelting, hydrometallurgical treatments of ores, ore roasting in ovens, coke ovens, thermal-electric generating stations, cracking of crude oils, pulp and paper production and steel manufacturing, to name only a few. It is important that at least H 2 S be removed from the gas stream before exhaust to atmosphere.
  • Various techniques have been developed to deal with the presence of H 2 S in a gas stream. For example, U.K.
  • Patent 1,376,830 discloses the removal of hydrogen sulphide from coke oven gas by way of a water scrubbing technique, where the water includes ammonium salts, iron sulphate, alkaline arsenite, alkaline arsenate or soda, as well as catalytic materials for converting the hydrogen sulphide to elemental sulfur.
  • Such technique develops complexes with the hydrogen sulphide, which in turn must be disposed off.
  • disposal presents a problem with the catalytic conversion technique of U.S. Patent 5,118,490, where it .is difficult to dispose of the vanadium and/or platinum catalyst.
  • Canadian patent 1,103,412 describes the recovery of hydrogen sulphide off gases, generated during the pulp bleaching process. It is generally stated that the hydrogen sulphide off gases, are oxidised to produce S0 3 , which is dissolved in a water solution to yield a sulfuric acid product. The generated sulfuric acid is then returned to the manufacturing process to make chlorine dioxide, which in turn, is used in the pulp bleaching process.
  • the preferred process for preparing sulfuric acid is the contact process, where S0 2 is oxidised to S0 3 in the gas phase, and the S0 3 then with water makes H 2 S0 4 .
  • Other processes to be considered are somewhat unconventional, for example, U.S Patent 2,342,704, describes the manufacture of an aqueous solution of sulfuric acid from sulfur dioxide, by passing through a gas absorbing zone, a stream of an aqueous absorbent solution containing manganese sulphate and a material selected from the group consisting of alkyl naphthalene sulphonic acids and the alkaline metal salts thereof. Both components are in relatively small amounts and in a concentration required for the maximum rate of conversion for the concentration of the aqueous solution of sulfuric acid being produced.
  • the process is accomplished by passing a stream of gas containing sulfur dioxide and oxygen in intimate contact with and countercurrent to the stream of aqueous absorbent solution in the zone and by withdrawing from the zone an aqueous solution of sulfuric acid containing up to approximately 40% by weight of sulfuric acid.
  • Such low percentage by weight of sulfuric acid is not that useful and would normally not be valuable for reuse in most of the major industrial applications.
  • U.S. Patent 3,042,489 describes a non-catalytic process for the production of sulfuric acid in high yield by oxidising sulfur in an aqueous dispersion to sulfur trioxide at a temperature between about 275 ⁇ C and 360 ⁇ C.
  • the reaction is carried out in a pressure vessel under a pressure sufficient to maintain some of the water in the liquid phase and recovering sulfuric acid from the oxidised product.
  • the contraction operation and maintenance of such a pressure vessel is expensive and would render the selling price of the product more expensive.
  • U.S. Patent 1,810,253 describes what the inventor (Petersen) believes is an improvement to the lead chamber process.
  • the improved process makes sulfuric acid at a concentration of about 60% by wt. or 12ml.
  • the patent describes higher concentrations, people skilled in the art knew that the thermodynamics and kinetics of the lead chamber process were incapable of making a higher concentration of sulfuric acid.
  • Petersen's process is carried out in the gas phase, that is a gaseous phase of S0 2 is contacted with a thin film liquid phase containing sulfuric and nitric acid to convert S0 2 into H 2 S0 4 at the interface of the thin film liquid and the large volume gaseous phase passing through the packed tower.
  • Petersen's contribution to the lead chamber process was to increase the surface area of the walls in the lead chamber process by providing very small tower packing.
  • the increased surface area of the thin film liquid thereby increased the interface with the gaseous phase to increase conversion of S0 2 into H 2 S0 4 .
  • any sulfuric acid manufacturing process produce concentrated sulfuric acid, typically having a concentration of H 2 S0 4 , greater than 80% and preferably in the range of 90% to 98%.
  • a preferred process is capable of processing H 2 S concentrations from a ppm amount up to 40% by weight in a gas stream. This has been very difficult for Prior Art processes to accomplish.
  • a process is now provided which converts in the liquid phase, a source of sulfur dioxide into sulfuric acid.
  • the process is capable of converting dilute to fairly concentrated sources of sulfur dioxide which may be generated by smelting processes or by the combustion of H 2 S or ercaptans to form sulfur dioxide plus various inerts.
  • a further advantage and feature of this invention is that the production of the sulfuric acid from a source of sulfur dioxide, does not produce any sulfur during the manufacturing process. Hence, there is no solid sulfur to contend with in any of the processing equipment.
  • a process for producing in a liquid phase, concentrated sulfuric acid from a source of sulfur dioxide.
  • the process comprises: i) converting in the liquid phase the source of sulfur dioxide to sulfuric acid, the liquid phase comprising: a) nitric acid at a sufficient concentration to commence in the liquid phase conversion in the presence of oxygen, of sulfur dioxide into sulfuric acid in the initial absence of sulfuric acid, or b) nitric acid at a sufficient concentration to maintain in the liquid phase conversion of sulfur dioxide in the presence of sulfuric acid either generated by said conversion or present at commencement of said conversion, and with the proviso that the concentration of nitric acid and sulfuric acid ranges from 0.1M to 16M where the concentration of nitric acid is at least 5M in the initial absence of sulfuric acid, and ii) introducing to the liquid phase a source of oxygen at a concentration sufficient to provide for the liquid phase catalytic conversion of S0 2 into H 2 S0 4 .
  • the source of sulfur dioxide is from burning H 2 S liquid or solid sulfur or sulfur containing organics
  • the heat of combustion is used to concentrate, if needed, the resultant liquid phase containing sulfuric acid, to produce highly concentrated sulfuric acid in the range of 90% and greater.
  • Figure l is a schematic showing the general layout of the components in which the process of this invention is carried out to produce a concentrated form of sulfuric acid.
  • the process in accordance with this invention has the facility to recover sources of sulfur dioxide or entities which can be converted to sulfur dioxide.
  • source of sulfur dioxide is intended to include any solid, liquid or gaseous form which contains or is convertible into a gaseous stream containing sulfur dioxide. This terminology is therefore intended to include sources such as simple gaseous, solid or liquid compounds containing sulfur because burning of such compounds produces sulfur dioxide.
  • the components are recovered from gaseous streams and the recovery is conducted in a liquid phase with conversion of the sulfur dioxide to a valuable product namely sulfuric acid.
  • the process is able to treat gas streams having from dilute to concentrated levels of sulfur dioxide due to the fact that the conversion is carried out in the liquid phase.
  • Other sources of sulfur dioxide include the burning of sulfur and sulfur containing organics.
  • the sulfur may be in the form of a liquid stream or a flow of solids.
  • Sulfur containing organics include mercaptans, polysulfides and sulfur containing amines.
  • H 2 S is particularly preferred as a component to be treated in accordance with the process of this invention, because prior processes which related to the conversion of H 2 S to less harmful components usually resulted in the production of sulfur which is unwanted for purposes of producing sulfuric acid.
  • sulfuric acid can be produced at a concentration which provides for valuable reuse.
  • the several advantages and features of this invention are achieved in the liquid phase catalytic conversion of an incoming source of S0 2 into sulfuric acid in the liquid phase.
  • the process in accordance with a preferred embodiment of this invention ensures the conversion of H 2 S into H 2 S0 4 without the formation of elemental sulfur, there is no difficulty with an explosive gas mixture entering the tower, particularly in the case of treating H 2 S, considerably less heat is generated within the mass transfer tower compared to other processes, while the majority of the heat in the instance of burning H 2 S is generated in the incinerator. This allows the system to operate at a considerably lower temperature and where it is desirable to burn the H 2 S, a significant advantage is provided in that the heat available from such incineration can be used to further concentrate the sulfuric acid generated in the liquid phase.
  • a system of this nature costs considerably less than the cost for providing a physical plant for the high temperature and usually high pressure contact process or the lead chamber process.
  • the physical plant of this invention only requires a hydrogen sulfide, sulfur containing organic or sulfur incinerating furnace with a sulfuric acid concentrator, normally in the form of a boiler, and one or more reactors preferably in the form of mass transfer towers, possibly in the range of two or more for the conversion of S0 2 to H 2 S0 4 .
  • the maximum number of trays in the tower may vary greatly but it is possible to have up to 25 trays or the mass transfer exchange equivalent thereof.
  • the process of this invention avoids the formation of any elemental sulfur, so that in designing the conversion towers, there is no consideration required in the handling of generated solids.
  • the liquid phase as developed in the reactor has a sufficient concentration of nitric acid to commence conversion, in the presence of oxygen, of sulfur dioxide into sulfuric acid.
  • an excess of oxygen is provided in the liquid phase to ensure conversion of substantially all, if not complete conversion of the incoming source of sulfur dioxide.
  • excess oxygen normally ensures a complete conversion of incoming sulfur dioxide.
  • the reactor which may be in the form of a tower having a plurality of trays can operate at close to atmospheric conditions. There is no requirement for an expensive pressure vessel or tower.
  • the tower could be run at ambient pressure at the bottom and 6 to 10 inches (of water) of vacuum at the top, but preferably would be run at 6 to 10 inches of water (0.014 atmospheres to 0.0245 atmospheres) pressure at the bottom and ambient pressure at the top. This is a significant cost saving because operating at more than two atmospheres, the cost is at least twice that compared to the modest operating pressures and temperatures of this invention.
  • the difference in cost and maintenance of an essentially ambient pressure vessel is less costly by at least half in capital cost and also in maintenance compared to low-pressure vessels because of costly sealing devices, gaskets and expensive piping, pumps and pressure fittings.
  • the tower of this invention can operate at minimum pressures of approximately 1/100 of an atmosphere and perhaps at a maximum of no more than 1/2 of an atmosphere.
  • the nitric acid is also at a sufficient concentration to maintain conversion of sulfur dioxide.
  • the combined concentration of nitric acid and sulfuric acid ranges from about 5M to 16M, where the concentration of nitric acid is at least about 5M in the initial absence of sulfuric acid.
  • the concentration of nitric acid and sulfuric acid in the liquid phase may be about 5M and greater.
  • the minimum concentration of nitric acid may be 5M and greater in the initial absence of sulfuric acid in the system.
  • nitric acid and sulfuric acid there can be a considerable variance in the relative concentrations of nitric acid and sulfuric acid.
  • concentrations of nitric acid and sulfuric acid will be at the optimum concentrations, which are in the range of 10 to 16 M for sulfuric acid and 0.1 to 5M for nitric acid.
  • the relative concentration may vary due to continuous generation of sulfuric acid.
  • the increasing sulfuric acid concentration is depleted or reduced by virtue of removing from the stirred reactor, a portion of the liquid phase.
  • the concentration of sulfuric acid will be its highest.
  • concentration of nitric acid from the top of the tower to the bottom of the tower may vary where at the top of the tower, there is sufficient concentration of nitric acid to effect the conversion of sulfur dioxide, in the presence of oxygen, to sulfuric acid and correspondingly sufficient concentration of nitric acid at the bottom of the tower to maintain such conversion, where there is a higher concentration of sulfuric acid.
  • An alternative reactor set up may be a plug flow reactor, where there is a co-current flow of the gaseous and liquid phases.
  • the nitric acid is at a sufficient concentration to initiate the conversion in the absence of any sulfuric acid.
  • the sulfuric acid concentration constantly increases till at the exit of the plug flow reactor, the concentration of sulfuric acid is at a maximum, for example, 16M where throughout the plug flow reactor the concentration of nitric acid has remained at a level to not only initiate conversion, but maintain conversion in the presence of sulfuric acid.
  • HN0 2 nitrous acid
  • the nitric acid in being reduced to HN0 2 may well act as or produce a catalyst at these concentration ranges to facilitate the conversion.
  • the conversion can take place at a liquid phase temperature ranging from 20 ⁇ C up to 150 ⁇ C.
  • Excellent conversion results have been achieved at HN0 3 concentrations less than 3M and at a temperature of less than 50 ⁇ C, preferably 30°C to 45 ⁇ C in the presence of at least 5M sulfuric acid.
  • carrying out the conversion in the liquid phase provides for the build up in the liquid phase of sufficient liquid phase catalyst to achieve a vigourous conversion of S0 2 into H 2 S0 4 .
  • Such build up of catalyst cannot be achieved in the thin film liquid of the prior art gaseous phase reaction.
  • Oxygen must be present in the liquid phase to facilitate the conversion of S0 2 to H 2 S0 4 , where it is thought that oxygen plays an important role in the conversion of developed NO' entities back to nitric acid. It has been found that very little nitric acid has to be added back into the system because of this homogeneous catalytic system which can only happen in this liquid phase reaction and not in the prior art gaseous phase reactions.
  • the desired concentration of nitric acid is between 0.5 and 5M. However, since the nitric acid functions overall as a homogeneous catalyst, we have found that the concentration of nitric acid in the liquid phase during normal operating conditions may range from 0.1M up to 16M. In the absence of sulfuric acid, the preferred concentration of nitric acid is at least 5M and possibly up to 16M to commence the conversion. As explained with respect to the proposed reaction mechanism, the minimum acid concentration of about 5M is required in order to drive the production of the N0 + ion. Otherwise, the reaction won't proceed rapidly.
  • the reaction proceeds at low concentrations of nitric acid in the presence of at least 5M sulfuric acid which is a good indication that the nitric acid is acting as a catalyst in the overall reaction, and that the losses of nitric acid are primarily due to gaseous nitric acid carried out with the purified gas stream or with removed concentrated sulfuric acid.
  • the process of this invention can be conducted at very economical temperatures up to 150°C and at the aforementioned very low pressures.
  • the concentrations of sulfuric acid and nitric acid are relatively high and will require special equipment, in terms of manufacturing facility, it is understood that several other existing processes deal with these concentrations of sulfuric and nitric acid.
  • the concentration of sulfuric acid used in the process is from 12 to 16M and correspondingly the nitric acid concentration is preferably in the range of 0.1M to 5M, when operating in the temperature range of 30 ⁇ C to 100 ⁇ C.
  • the physical requirements for the reactor physical plant systems can be of less expensive materials.
  • any sulfur containing amines would additionally be converted to S0 2 which is converted in accordance with the subject process.
  • the reaction in the liquid phase over a series of mass transfer interface plates does not appear to have any limitations, kinetically or thermodynamically as evidenced by the fairly broad range at which the acid concentrations may exist, the oxygen concentration in the incoming source thereof, being sufficient to react fully with the S0 2 stream and the temperatures and pressures at which the process is effective while the prior art contact process and lead chamber process have such limitations.
  • FIG. 1 is a schematic of one suggested physical plant in which the process may be carried out.
  • the physical plant 10 comprises an incinerator 12, a sulfuric acid concentrator 14, a mass transfer column 16, heat exchanger 18 and pumps 20 and 22.
  • An incoming gas stream to be treated is introduced in the direction of arrow 24 to conduit 26, which has an offset , T' section 28, which leads into the incinerator 12 through the bottom wall portion 30. If the incoming gas stream 24 contains H 2 S, it is desirable to combust the H 2 S in the incinerator 12. It is understood that the incoming gas stream may have sufficient oxygen to support combustion.
  • the incoming stream 32 may also be oxygen fortified air or pure oxygen, depending upon the amount of oxygen required to ensure combustion of H 2 S in forming the desired S0 2 gas stream.
  • Combustion is supported within the incinerator 12 in the lower region 34, where combustion continues in the direction of arrow 36 to produce an exhaust stream comprising S0 2 , which is removed through the incinerator via conduit 38 in the direction of arrow 40.
  • the incinerator 12 includes within its outer wall portion 42, the sulfuric acid concentrator 14.
  • the sulfuric acid concentrator 14 comprises a vessel 44, with interior wall 46.
  • An inlet 48 to the bottom 50 of the vessel introduces a portion of the liquid phase withdrawn from the tower 16 through line 52 in the direction of arrow 54.
  • the liquid phase is withdrawn from the bottom portion of the tower 16 in the manner to be discussed.
  • the liquid phase 56, within the concentrator 14, is heated by the heat of combustion of the incoming gas stream, to heat the liquid phase to a temperature where water and any remaining nitric acid and other nitrogen components are boiled off of the liquid phase 58, with a gas stream exiting exhaust conduit 60 in the direction of arrow 62.
  • the sulfuric acid which does not boil off in the liquid phase, instead continues to be concentrated within the concentrator vessel 44, until it achieves the desired concentration of perhaps 90% or greater, and preferably 98% or greater.
  • the concentrated sulfuric acid from the concentrator 14 is removed via conduit 64, which travels in the direction of arrow 66 and is introduced to the suction side of pump 22.
  • Pump 22 delivers the concentrated sulfuric acid through heat exchanger 18, where a coolant is introduced at 68 and is removed at 70, to reduce the temperature of the concentrated sulfuric acid to less than 150°C.
  • the concentrated sulfuric acid then leaves the heat exchanger 18 through conduit 72 in the direction of arrow 74. A portion of that concentrated sulfuric acid is diverted through 'T' section with conduit 76, for introducing it back into the column 16, in the direction of arrow 78.
  • the stream of S0 2 source to be treated moves through conduit 38, in the direction of arrow 40 into the lower portion 84 of the tower 16 through inlet 86.
  • the incoming stream of sulfur dioxide is mixed at juncture 88 with a source of oxygen introduced in the direction of arrow 90 into conduit 92, and is compressed to the desired low pressure through pump 20 and directed in the direction of arrow 94 to the juncture 88 through conduit 96.
  • Sufficient oxygen is supplied in the incoming stream of S0 to ensure conversion of S0 2 into H 2 S0 4 by oxidising the nitrosyl group to regenerate nitric acid.
  • the gas stream at a sufficiently low pressure, for example, to bubble upwardly through the mass transfer plates 98 in the direction of arrows 100.
  • the liquid phase which travels downwardly of the mass transfer plates is shown schematically at 102 on each plate or tray 98.
  • tray 98 is perforated to include openings 104 which permit the gases to bubble upwardly through the downwardly flowing or countercurrently flowing liquid phase 102.
  • Suitable downcomers 106 are provided on each tray, to permit liquid to flow from each tray to the next tray. Furthermore, the height of the downcomers determines the height of liquid above each tray.
  • one or more downcomers may be provided on each tray and also that the size of the perforations 104 on each tray are selected to support the necessary amount of liquid above the tray, without passing through the openings and at the same time, allow sufficient time for the gases bubbling through the liquid phase 102 to react and achieve conversion of the developed S0 3 from S0 2 to
  • the tower 16 is exemplary of any type of mass transfer column that might be used, this system is preferred from the stand point of materials of construction and cost of manufacture and erection. It is understood that other types of mass transfer systems may be used such as packed columns with packing immersed in liquid, combination of packing with trays and the like. The gases as they flow upwardly through the column 16 are gathered and removed through outlet 108 in conduit 110 in the direction of arrow 112.
  • conduit 114 As directed to the suction side of pump 20, withdraws a portion of the treated gases for recycle in direction of arrow 116.
  • Such recycled gas and possibly some make-up water in the form of steam (as required to control acid concentration) is combined with the incoming source of oxygen through conduit 92 before being compressed in pump 20 to the operating pressure which as previously mentioned is normally in the range of 1/4 to 1/2 an atmosphere.
  • the downcoming liquid is gathered at the base of tower 16, preferably in a tower well 118. Liquid is extracted from the well 118 through liquid outlet 120, which is delivered in the direction of arrow 54 to the conduit 52 for concentration in the concentrator 14.
  • a suitable mass balance is applied to the system, where liquid withdrawn from column 16 is equivalent to the rate of introduction of liquid to the column through conduit 76, once the system has reached steady state operation.
  • Make up nitric acid to column 16 may be determined based on the amount of nitric acid lost through stack 60 of concentrator 14 in the direction of arrow 62. It is appreciated that a suitable heat exchanger may be provided in line 60 to condense the off gases and return in liquid phase captured nitric acid that has been boiled off in the concentrator 14. That captured nitric acid may also be reintroduced to the column 16 through line 122 for recycle purposes.
  • the nitric acid in the liquid phase is in essence diluted by the production of the sulfuric acid, however, nitric acid is not used up in the process.
  • Additional experimental runs were carried out at reduced concentrations of nitric acid in the range of 0.1M to 1M and in the initial presence of sulfuric acid of at least 5M. At these lower concentrations of nitric acid and at either room or elevated temperature, conversion of S0 2 to H 2 S0 4 was achieved.
  • the concentration of sulfuric acid, at commencement may be below the desired minimum of 10M.
  • the reaction proceeds and preferably the concentration of sulfuric acid is at least 5M when the nitric acid concentration is at a lower level, at the commencement so that the reaction proceeds quickly and the build up of sulfuric acid to the desired level occurs.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Treating Waste Gases (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

Procédé de production en phase liquide, d"acide sulfurique concentré en phase liquide à partir d"une source de dioxyde de sulfure. Le procédé consiste à convertir la source de dioxyde de sulfure en acide sulfurique. La phase liquide comprend a) de l"acide nitrique en concentration suffisante pour que la conversion puisse de dioxyde de sulfure en acide sulfurique puisse commencer en présence d"oxygène et en l"absence initiale d"acide sulfurique; b) de l"acide nitrique en concentration suffisante pour que la conversion de dioxyde de sulfure soit maintenue en présence d"acide sulfurique généré par ladite conversion ou présent au début de la conversion; et c) une concentration combinée d"acide nitrique et d"acide sulfurique de 5 à 16M, la concentration d"acide nitrique étant d"au moins 5M en l"absence initiale d"acide sulfurique, et une source d"oxygène étant introduite dans la phase aqueuse en concentration suffisante pour que cette conversion catalytique de SO2 en H2SO4 ait lieu.
PCT/CA1996/000196 1995-03-27 1996-03-27 Conversion en phase liquide d"une source de dioxyde de sulfure en acide sulfurique WO1996031262A2 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
PL96322447A PL322447A1 (en) 1995-03-27 1996-03-27 Liquid-phase conversion of sulphur dioxide into sulphuric acid
AU51406/96A AU704392B2 (en) 1995-03-27 1996-03-27 Liquid phase conversion of a source of sulfur dioxide to sulfuric acid
BR9607990-8A BR9607990A (pt) 1995-03-27 1996-03-27 Conversão em fase lìquida de uma fonte de dióxido de enxofre a ácido sulfúrico.
JP8529813A JPH11503105A (ja) 1995-03-27 1996-03-27 二酸化硫黄源の硫酸への液相変換
CA002216432A CA2216432C (fr) 1995-03-27 1996-03-27 Conversion en phase liquide d'une source de dioxyde de sulfure en acide sulfurique
EP96907976A EP0839117A2 (fr) 1995-03-27 1996-03-27 Conversion en phase liquide d'une source de dioxyde de sulfure en acide sulfurique
NO974468A NO974468L (no) 1995-03-27 1997-09-26 Omforming av væskefase fra en kilde av svoveldioksid til svovelsyre

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US41095795A 1995-03-27 1995-03-27
US08/410,957 1995-03-27

Publications (2)

Publication Number Publication Date
WO1996031262A2 true WO1996031262A2 (fr) 1996-10-10
WO1996031262A3 WO1996031262A3 (fr) 1996-12-12

Family

ID=23626963

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CA1996/000196 WO1996031262A2 (fr) 1995-03-27 1996-03-27 Conversion en phase liquide d"une source de dioxyde de sulfure en acide sulfurique

Country Status (12)

Country Link
US (1) US5788949A (fr)
EP (1) EP0839117A2 (fr)
JP (1) JPH11503105A (fr)
KR (1) KR19980703355A (fr)
CN (1) CN1181743A (fr)
AU (1) AU704392B2 (fr)
BR (1) BR9607990A (fr)
CA (1) CA2216432C (fr)
CZ (1) CZ302997A3 (fr)
NO (1) NO974468L (fr)
PL (1) PL322447A1 (fr)
WO (1) WO1996031262A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103303877A (zh) * 2013-07-03 2013-09-18 中国瑞林工程技术有限公司 多气源低浓度so2烟气综合回收制酸工艺流程

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1076215C (zh) * 1999-08-13 2001-12-19 丁华 硫酸装置两次转化的互补换热流程
US6497382B2 (en) * 2001-01-02 2002-12-24 Michael R. King Cord holder
US20030086846A1 (en) * 2001-11-05 2003-05-08 Adusei George Y. Monolith stacking configuration for improved flooding
US7032894B2 (en) * 2001-11-05 2006-04-25 Corning Incorporated Flow distributor for monolith reactors
US7416716B2 (en) * 2005-11-28 2008-08-26 Air Products And Chemicals, Inc. Purification of carbon dioxide
US20080025910A1 (en) * 2006-07-27 2008-01-31 O'brien Robert Neville Process to make both nitric and sulfuric acid
CN111830012A (zh) * 2020-07-01 2020-10-27 新兴铸管股份有限公司 测定铁矿石中硫含量的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2562240A (en) * 1944-03-11 1951-07-31 Allied Chem & Dye Corp Manufacture of oleum
US3042489A (en) * 1958-11-20 1962-07-03 Sterling Drug Inc Production of sulfuric acid
GB1513516A (en) * 1976-06-08 1978-06-07 Inst Khim Fiz An Sssr Process for the production of sulphuric acid
DE4019184A1 (de) * 1989-06-21 1991-01-03 Monsanto Co Verfahren zur herstellung von schwefelsaeure

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1810253A (en) * 1923-03-13 1931-06-16 Petersen Hugo Manufacture of sulphuric acid
US2125143A (en) * 1936-01-24 1938-07-26 Du Pont Process of recovering sulphuric acid from hot gas mixtures containing sulphur oxides
GB503643A (en) * 1937-12-24 1939-04-12 William Warren Triggs Process for the manufacture of sulphuric acid
GB736146A (en) * 1950-12-30 1955-09-07 Alfons Zieren Improvements in or relating to the manufacture of sulphuric acid
JPS5643771B2 (fr) * 1973-12-18 1981-10-15
JPS5229469A (en) * 1975-09-01 1977-03-05 Nippon Oil Co Ltd Method of removing so2 in gas containing so2
DE3531406A1 (de) * 1985-09-03 1987-03-05 Herbert Kueppenbender Verfahren und vorrichtung zur rauch- und abgasreinigung mittels nassverfahren
SU1699900A1 (ru) * 1989-06-09 1991-12-23 Воскресенский филиал Научно-исследовательского института по удобрениям и инсектофунгицидам им.проф.Я.В.Самойлова Научно-производственного объединения "Минудобрения" Способ пуска установки дл получени серной кислоты нитрозным методом

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2562240A (en) * 1944-03-11 1951-07-31 Allied Chem & Dye Corp Manufacture of oleum
US3042489A (en) * 1958-11-20 1962-07-03 Sterling Drug Inc Production of sulfuric acid
GB1513516A (en) * 1976-06-08 1978-06-07 Inst Khim Fiz An Sssr Process for the production of sulphuric acid
DE4019184A1 (de) * 1989-06-21 1991-01-03 Monsanto Co Verfahren zur herstellung von schwefelsaeure

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103303877A (zh) * 2013-07-03 2013-09-18 中国瑞林工程技术有限公司 多气源低浓度so2烟气综合回收制酸工艺流程

Also Published As

Publication number Publication date
EP0839117A2 (fr) 1998-05-06
KR19980703355A (ko) 1998-10-15
US5788949A (en) 1998-08-04
CZ302997A3 (cs) 1998-05-13
CA2216432A1 (fr) 1996-10-10
AU704392B2 (en) 1999-04-22
PL322447A1 (en) 1998-02-02
NO974468L (no) 1997-11-26
BR9607990A (pt) 2000-04-18
MX9707397A (es) 1998-06-28
CA2216432C (fr) 2003-12-02
JPH11503105A (ja) 1999-03-23
NO974468D0 (no) 1997-09-26
WO1996031262A3 (fr) 1996-12-12
CN1181743A (zh) 1998-05-13
AU5140696A (en) 1996-10-23

Similar Documents

Publication Publication Date Title
EP1142628A2 (fr) Traitment de flux gazeux contenant du sulfure d'hydrogéne
JP3300009B2 (ja) ガスの処理方法
US7544344B2 (en) Process for recovering sulphur from a gas stream containing hydrogen sulphide
EP3963260B1 (fr) Procédé de production de soufre élémentaire et d'acide sulfurique
MXPA01008336A (es) Tratamiento de una corriente de gas que contiene sulfuro de hidrogeno.
US6569398B2 (en) Method for treating hydrogen sulfide-containing waste gases
US5788949A (en) Liquid phase conversion of a source of sulfur dioxide to sulfuric acid
US4419337A (en) Process and apparatus for reacting sulphur-containing material with oxidizing gas
EP1456123B1 (fr) Procede de recuperation de constituants sulfureux dans un processus de recuperation de soufre
RU2474533C1 (ru) Способ получения элементной серы из отходящего газа, содержащего диоксид серы
US6030592A (en) Process for the desulfurization of sulfur dioxide-containing gases
US4693881A (en) Simultaneous separation and conversion to sulfur of H2 S
US4241041A (en) Methods for the recovery of sulfur components from flue gas and recycle sodium sulfite by reduction-smelting and carbonating to strip hydrogen sulfide
US4960575A (en) Removal of hydrogen sulfide with on site generated sulfite from geothermal steam
EA026172B1 (ru) Поэтапное сжигание сернистых горючих отходящих потоков с извлечением серы по способу клауса
MXPA97007397A (en) Conversion in liquid phase of a source of sulfur dioxide in acid sulfur
Wermink et al. Vitrisol® a 100% selective process for H2S removal in the presence of CO2
RU2669606C2 (ru) Обработка газов
US2588331A (en) Recovery of alkylation sludge acids
EP0561521A1 (fr) Traitement de déchets ou d'autres matériaux
CA2154598C (fr) Procede d'extraction de la vapeur d'eau
EP0050527A1 (fr) Procédé et dispositif pour la réaction d'un matériau contenant du soufre avec un gaz oxydant

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 96192844.1

Country of ref document: CN

AK Designated states

Kind code of ref document: A2

Designated state(s): AL AM AT AU AZ BB BG BR BY CA CH CN CZ DE DK EE ES FI GB GE HU IS JP KE KG KP KR KZ LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TR TT UA UG UZ VN AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML

AK Designated states

Kind code of ref document: A3

Designated state(s): AL AM AT AU AZ BB BG BR BY CA CH CN CZ DE DK EE ES FI GB GE HU IS JP KE KG KP KR KZ LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TR TT UA UG UZ VN AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A3

Designated state(s): KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref document number: 2216432

Country of ref document: CA

Ref document number: 2216432

Country of ref document: CA

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: PV1997-3029

Country of ref document: CZ

WWE Wipo information: entry into national phase

Ref document number: PA/a/1997/007397

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 1019970706760

Country of ref document: KR

ENP Entry into the national phase

Ref document number: 1996 529813

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1996907976

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWP Wipo information: published in national office

Ref document number: 1996907976

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: PV1997-3029

Country of ref document: CZ

WWP Wipo information: published in national office

Ref document number: 1019970706760

Country of ref document: KR

WWR Wipo information: refused in national office

Ref document number: PV1997-3029

Country of ref document: CZ

WWW Wipo information: withdrawn in national office

Ref document number: 1019970706760

Country of ref document: KR

WWR Wipo information: refused in national office

Ref document number: 1996907976

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1996907976

Country of ref document: EP